JPH07330903A - Polyarylene thioehter and its production - Google Patents

Abstract

PURPOSE:To obtain a branched uncured polyarylene thioether with improved mechanical characteristics without detriment to flash characteristics, melt stability, and color matching properties by selecting a polyarylene thioether with specified physical properties. CONSTITUTION:A polyarylene thioether is selected which mainly comprises repeating units represented by the formula and has a Hunter whiteness of 20% or higher, a wt. average mol.wt. of 200,000=1,000,000, a melt viscosity eta*1000 of 20-500Pa.s, and a shear rate dependence of melt viscosity eta*100/eta*1000 of 1.8-4.0. The melt viscosity eta*1000 is a melt viscosity obtd. at 316 deg.C at a shear rate of 1,000sec<-1> using Capirograph equipped with a nozzle with an inside diameter of 0.50mm and a length of 5.00mm. The shear rate dependence is the ratio of a melt viscosity at 316 deg.C at a shear rate of 100sec<-1> measured with the Capirograph to that at 316 deg.C at a shear rate of 1,00sec<-1>. The polymer is produced without using an auxiliary such as lithium chloride or benzoate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyarylene thioether having improved mechanical properties, and more specifically, it has a large weight average molecular weight, high melt flowability and melt rate dependence on shear rate, and The present invention relates to a branched, uncured polyarylene thioether having excellent color matching property and melt stability. The present invention also relates to a method for producing the above polyarylene thioether in a granular form. Furthermore, the present invention relates to a resin composition containing the above polyarylene thioether.

[0002]

2. Description of the Related Art Polyarylene thioether (hereinafter referred to as P
ATE) is an engineering plastic with excellent heat resistance, mechanical properties, chemical resistance, injection moldability, etc., and is used in a wide range of fields such as the electronic / electrical industry field, automobile aircraft industry field, and precision machine industry field. ing. PAT
E can be produced by various methods, but a method of reacting an alkali metal sulfide with a dihaloaromatic compound in a polar solvent is common.

By the way, the PATE that was initially developed was
After obtaining a polymer having a low degree of polymerization by polymerization, the polymer was heated in the presence of air to partially cross-link it to increase the molecular weight (for example, US Pat. No. 3,35,35).
4,129). Oxidation-crosslinking type (cure type) PATE obtained by oxidatively crosslinking (curing) such a polymer having a low degree of polymerization has a remarkable coloring, and thus it is difficult to adjust to an arbitrary color. Since the melt stability is low, there is a problem that melt processing such as injection molding is difficult, and the mechanical strength of the obtained molded product is not sufficient.

On the other hand, in recent years, methods for obtaining high molecular weight PATE during polymerization have been developed (for example, US Pat. No. 3,919,177 and US Pat. No. 4,645,8).
No. 26). According to these methods, a linear and high molecular weight P is obtained by the polymerization reaction without curing after the polymerization.
ATE can be obtained. The straight chain / uncure type PATE obtained by these methods has a low degree of coloring, easy color adjustment, and excellent melt stability. It is also characterized by high strength. However, linear PATE
However, there is a problem in that many burrs are generated during injection molding.

Recently, in order to improve the burr properties, a slight stoichiometric excess of dihaloaromatic compound with respect to alkali metal sulfide is used in the polymerization, and at the same time, it has three or more reactive groups. It has been proposed that an aromatic compound be present to produce a branched / uncured PATE having a weight average molecular weight of 200,000 or less (Japanese Patent Laid-Open No. 2-45532).
No. 2,294,331, US Pat. No. 5,23.
No. 1,163). These conventional branched / uncured PAs
Although TE has improved burr characteristics, it has a problem that mechanical properties are insufficient in practical use.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a PATE having improved mechanical properties while maintaining the burr properties, melt stability and toning property of the branched / uncured PATE. is there. Further, an object of the present invention is to provide a branched / uncured PATE having the above-mentioned excellent characteristics,
It is an object of the present invention to provide a method which can be produced at a relatively low cost without using an expensive auxiliary agent (eg, lithium chloride, lithium benzoate, etc.). Another object of the present invention is a branched / uncured PA having the excellent characteristics as described above.
It is to provide a resin composition containing TE.

The inventors of the present invention have conducted extensive studies to overcome the problems of the prior art, and as a result, in the method for producing PATE by reacting a dihaloaromatic compound with an alkali metal sulfide, three or more PATEs are produced. Polymerization reaction under the specific conditions in the presence of polyhaloaromatic compounds having halogen substituents, has high fluidity and high shear rate dependence, and has burr properties, melt stability, and color matching properties. It was found that a branched and uncured PATE having a high molecular weight, which is excellent in mechanical properties and improved, can be obtained. According to the production method of the present invention, a branched / uncured PATE having a weight average molecular weight of more than 200,000 is used without using an expensive polymerization aid.
Can be obtained in the form of granules having good handleability.
The present invention has been completed based on these findings.

[0008]

According to the present invention, the following repeating unit:

[0009]

[Chemical 2] A polyarylene thioether whose main component is,

(A) Hunter whiteness of 20% or more,
(B) the weight average molecular weight is more than 200,000 and less than 1,000,000,
(C) Melt viscosity η ^* ₁₀₀₀ is 20 to 500 Pa · s, and (d) Shear rate dependence η ^* ₁₀₀ / η ^* _{1000 of} melt viscosity is 1.8 to 4.0, polyarylene. A thioether is provided. [However, melt viscosity η ^*
₁₀₀₀ is the melt viscosity measured at a shear rate of 1000 (1 / sec) at 316 ° C. using a capillograph equipped with a nozzle having an inner diameter of 0.50 mmφ and a length of 5.00 mm. The shear rate dependence η ^* ₁₀₀ / η ^* ₁₀₀₀ of the melt viscosity was determined by using the above capillograph at 316 ° C. and a shear rate of 100 (1 /
Sec) and 1000 (1 / sec), respectively, is the ratio of the melt viscosities η ^* ₁₀₀ and η ^* ₁₀₀₀ measured. Further, according to the present invention, there is provided a resin composition containing 25 to 98% by weight of the above polyarylene thioether and 2 to 75% by weight of a fibrous filler.

Furthermore, according to the present invention, an alkali metal sulfide and a dihaloaromatic compound are reacted in a water-containing organic amide solvent in the presence of a polyhaloaromatic compound having three or more halogen substituents, In the method for producing a polyarylene thioether having a branched structure, the following steps (1) to (3) are sequentially performed to provide a method for producing a polyarylene thioether.

(1) First-stage polymerization step: Based on the charged amount of alkali metal sulfide of 100 mol, 90 to 120 mol of dihalo aromatic compound, 0 to 20 mol of monohalo aromatic compound, and 3 or more halogen substitutions. A polyhaloaromatic compound having a group of 0.1 to 5.0
It is charged at each molar ratio and the coexisting water content is 30 to 24.
Keep at 0 mole ratio and at least 1 at 150-270 ° C
Heat for hours to form a prepolymer.

(2) Second-stage polymerization step The coexisting water content of the reaction system containing the prepolymer is 2 based on the charged amount of alkali metal sulfide of 100 mol.
The liquid-liquid phase separation state mainly consisting of the polymer-containing phase and the other phase is maintained by adjusting the ratio to 45 to 800 mol, and the mixture is heated at 230 to 280 ° C for at least 0.5 hours. To continue the polymerization.

(3) Recovery step After completion of the polymerization, the reaction mixture is cooled under high speed stirring to a temperature not higher than the glass transition temperature of the produced polymer, and the produced polymer is a granule having an average particle diameter of 0.1 to 4.0 mm. Collect in a form. The polyarylene thioether of the present invention is a branched and uncured polymer which has a branched structure derived from a polyhaloaromatic compound having three or more halogen substituents and is not cured.

The present invention will be described in detail below. PATE The PATE of the present invention is a reaction of an alkali metal sulfide and a dihalo aromatic compound in a water-containing organic amide solvent in the presence of a polyhalo aromatic compound having 3 or more halogen substituents under specific conditions. It can be manufactured by A polyhaloaromatic compound having 3 or more halogen substituents acts as a crosslinking agent. Therefore,
The PATE of the present invention is a polymer having a branched structure derived from a polyhaloaromatic compound having 3 or more halogen substituents. Here, the branched structure means not only the case where the polymer chain is branched, but also the case where a crosslinked structure is formed. A small amount of a monohaloaromatic compound may be present in the polymerization reaction, if desired.

The PATE of the present invention has a branched structure introduced into its molecular chain, but its composition is very uniform. It is presumed that the reason is that according to the production method of the present invention, a structure in which the branched PATE portions having a large molecular weight are uniformly distributed is formed in the matrix of the linear PATE. Therefore, the PATE of the present invention is not affected by processing conditions such as melt-kneading, and various physical properties are stable.

The PATE of the present invention, in the molten state,
When a high shear rate is applied, the branched PATE part plastically deforms in the flow direction, so that the apparent melt viscosity is kept relatively low, while at a low shear rate, the apparent melt viscosity is significantly increased. At low shear rates,
It is presumed that this is because the apparent melt viscosity is remarkably increased by elastically recovering from the plastically deformed state within a certain range. It can be considered that such a mechanism suppresses the occurrence of burrs during injection molding. The PATE of the present invention can be obtained as a polymer having a sufficiently high molecular weight and excellent mechanical properties by devising a polymerization method.

The features of the PATE of the present invention will be described more specifically as follows. (1) The PATE of the present invention is a branched polymer, but the degree of coloring is small and color matching is easy. It is a characteristic of uncured PATE that it has a toning property, and it is difficult to adjust it to an arbitrary color in the oxidatively cross-linked cured PATE, because it is markedly colored. The toning property of a polymer can be evaluated by Hunter whiteness. In PATE of the present invention, the neat resin melt-molded product (amorphous sheet having a thickness of about 0.3 mm) has a Hunter whiteness of 20% or more, preferably 30.
% Or more, more preferably 35% or more, and the color matching property is excellent.

(2) The PATE of the present invention has a weight average molecular weight of more than 200,000 and less than 1 million, preferably 250,000.
It is in the range of less than 0,000. The weight average molecular weight of PATE is 2
If it is less than 0,000, the mechanical properties (flexural strength, impact resistance, etc.) of the injection-molded product obtained by using the PATE are likely to be insufficient. On the other hand, when the weight average molecular weight of PATE is 1,000,000 or more, the melt viscosity becomes too high, which may make it unsuitable for injection molding.

(3) PATE of the present invention is a polymer exhibiting high fluidity under a high shear rate. This property is due to the fact that PATE of the present invention is a branched polymer.
It is difficult to obtain such properties with the linear PATE. The PATE of the present invention has a shear rate of 1 at 316 ° C.
Melt viscosity η ^* ₁₀₀₀ measured at 000 (1 / sec) is 20-
It is in the range of 500 Pa · s, preferably 30 to 400 Pa · s, and more preferably 50 to 300 Pa · s. That is, it is a polymer having a relatively low melt viscosity under high temperature and high shear rate. Therefore, the PATE of the present invention has a high melt fluidity and is a polymer particularly suitable for injection molding. Further, since the melt viscosity is moderate, the mechanical strength of the molded product such as impact resistance is good. If the melt viscosity η ^* ₁₀₀₀ of PATE is less than 20 Pa · s, the mechanical properties and burr characteristics of the injection-molded product obtained using this PATE may be unsatisfactory. If it exceeds 500 Pa · s, the viscosity is too high. , It may not be suitable for injection molding.

(4) In the PATE of the present invention, the shear rate dependence of the melt viscosity defined above is η ^* ₁₀₀ / η ^* ₁₀₀₀ of 1.8.
˜4.0, preferably 2.0 to 3.5, and more preferably 2.3 to 3.0. The PATE of the present invention has a very high melt viscosity in the low shear rate range and a very low melt viscosity in the high shear rate range. If the shear rate dependency is less than 1.8, the effect of improving the burr property is not sufficient, while if it exceeds 4.0, the polymer becomes an excessively branched polymer and the mechanical properties of the molded product are insufficient. There is a risk that

(5) The PATE of the present invention can be obtained in the form of granules having an average particle size of 0.1 to 4.0 mm, preferably 0.2 to 2.0 mm. Therefore, compared to powdery or lumpy polymers, purification after polymerization (removal of unreacted monomers, by-products, oligomers, washing,
The operation such as filtration) is easy, and the operability of transportation, weighing, kneading, etc. is excellent.

(6) In the PATE of the present invention, a glass short fiber having an average diameter of 10 μm (length 0.5 to 5 mm,
When a resin composition obtained by kneading (preferably about 3 mm) at a ratio of 40% by weight is injection-molded, the bending strength is 15 k.
g / mm ² or more, preferably 18 kg / mm ² or more, more preferably 20 kg / mm ² or more and Izod impact strength of 5 kg · cm / cm or more, preferably 6 kg · cm
/ Cm or more, more preferably 6.5 kg · cm / cm or more injection molded product having physical properties can be provided. Even in the case of branched / uncured type PATE, if the bending strength of the injection-molded product as described above is less than 15 kg / mm ² , the practical mechanical strength is unsatisfactory and the Izod impact strength is 5 kg.・ If it is less than cm / cm, the practical impact resistance is still unsatisfactory.

Method for producing PATE Branched / uncured P with improved mechanical properties of the present invention
ATE is produced by reacting an alkali metal sulfide and a dihalo aromatic compound in a water-containing organic amide solvent in the presence of a polyhalo aromatic compound having 3 or more halogen substituents under specific conditions. can do. If desired, a monohalo aromatic compound may coexist. In addition, it is practically sufficiently high without adding expensive polymerization aids such as alkali metal carboxylates, alkaline earth metal carboxylates, alkali metal halides and alkaline earth metal halides. A branched and uncured PATE having a molecular weight can be produced. Of course, if desired, these polymerization aids may be added, but normally, water can be made to act as a kind of polymerization aid by adjusting the amount of coexisting water.

The branched / uncured PATE of the present invention is
For example, it can be manufactured by the following manufacturing method.
That is, when reacting an alkali metal sulfide and a dihaloaromatic compound in a water-containing organic amide solvent in the presence of a polyhaloaromatic compound having three or more halogen substituents,
A branched / uncured PATE can be manufactured sequentially by the following steps (1) to (3).

(1) First-stage Polymerization Step 90-120 moles of dihalo aromatic compound, 0-20 moles of monohalo aromatic compound, and 3 or more halogen substitutions based on 100 moles of the charged amount of alkali metal sulfide. A polyhaloaromatic compound having a group of 0.1 to 5.0
It is charged at each molar ratio and the coexisting water content is 30 to 24.
Keep at 0 mole ratio and at least 1 at 150-270 ° C
Heat for hours to form a prepolymer.

(2) Second-stage polymerization step The amount of coexisting water in the reaction system containing the produced prepolymer is adjusted to a ratio of 245 to 800 mol based on 100 mol of the charged amount of alkali metal sulfide. Thereby, the liquid-liquid phase separation state mainly composed of the polymer-containing phase and the other phase is maintained,
Polymerization is continued by heating at 0 ° C. for at least 0.5 hours.

The post-polymerization step increases the molecular weight of the prepolymer produced in the pre-polymerization step. Therefore,
A phase containing a polymer mainly means immediately after the initiation of the second-stage polymerization, a phase containing a prepolymer produced in the first-stage polymerization, and after the initiation of the second-stage polymerization, the molecular weight of the prepolymer increases to a high-molecular weight polymer. Therefore, it means a phase containing these prepolymers and the produced polymer, and in the final stage, a phase mainly containing the produced polymer.

(3) Recovery step After completion of the polymerization, the reaction mixture is cooled under high-speed stirring until the temperature becomes equal to or lower than the glass transition temperature of the produced polymer, and the produced polymer is granulated with an average particle diameter of 0.1 to 4.0 mm. Collect in a form.

The method for producing PATE of the present invention can be said to be a phase-separation polymerization method because the polymerization is carried out while maintaining the liquid-liquid phase separation state particularly in the latter-stage polymerization step. According to this phase-separation polymerization method, a high molecular weight branched / uncured PATE can be easily obtained by adjusting the amount of coexisting water without using an expensive polymerization aid as described above.

Details of the raw materials and auxiliary raw materials used in the production method of the present invention are as follows. Examples of water include hydration water of alkali metal sulfide, added water, reaction water, water of an alkali metal sulfide aqueous solution, and the like. Examples of the organic amide solvent include N-methylpyrrolidone, N-ethylpyrrolidone, N, N-dimethylformamide, N, N
-Dimethylacetamide, N-methylcaprolactam,
Examples thereof include dimethylimidazolidinone, tetramethylurea, hexamethylphosphonic acid amide and the like. Among these, N-methyl-2-pyrrolidone (NMP) is particularly preferable from the viewpoint of economy and stability.

Examples of alkali metal sulfides include sodium sulfide, potassium sulfide, lithium sulfide, rubidium sulfide, cesium sulfide, and mixtures thereof. Further, the alkali metal sulfide may be generated in situ in a reaction vessel by a conventional method. These alkali metal sulfides can be used in the form of hydrates, aqueous mixtures or anhydrides. To react with the alkali metal disulfides and alkali metal thiosulfates present in trace amounts in the alkali metal sulfides, add a small amount of alkali metal hydroxides to remove these impurities, or convert them to sulfides. It may be converted. Of these, sodium sulfide is the cheapest and is industrially preferable.

Examples of the dihaloaromatic compound include p
Dihalobenzenes such as -dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, p-dibromobenzene; 2,5-dichlorotoluene, 1-methoxy-2,5
-Substituted dihalobenzenes such as dichlorobenzene; 1,4-
Dihalonaphthalene such as dichloronaphthalene; 4,4′-
Dihalobiphenyl such as dichlorobiphenyl and 3,3′-dichlorobiphenyl; Dihalobenzoic acid such as 3,5-dichlorobenzoic acid; Dihalobenzophenone such as 4,4′-dichlorobenzophenone; 4,4′-Dichlorodiphenyl sulfone , 3,3'-dichlorodiphenyl sulfone and other dihalodiphenyl sulfones; 4,4'-dichlorodiphenyl ether and other dihalodiphenyl ethers; and the like.

Of these, dihalobenzene is preferable from the viewpoints of economy and physical properties of the produced PATE, and particularly,
More preferred are p-dihalobenzenes such as p-dichlorobenzene. In particular, p-dihalobenzene, preferably 7
It is preferably contained in an amount of 0% by weight or more, more preferably 80% by weight or more, still more preferably 90 to 100% by weight. This gives a PATE with p-phenylene sulfide units as the main constituent. Further, as the fluidity improver, o-dihalobenzene, dihalodiphenyl ether and the like are effective.

Examples of the polyhaloaromatic compound having three or more halogen substituents include 1,2,3-trichlorobenzene, 1,2,3-tribromobenzene, 1,
2,4-trichlorobenzene, 1,2,4-tribromobenzene, 1,3,5-trichlorobenzene, 1,3
Trihalobenzenes such as 5-tribromobenzene and 1,3-dichloro-5-bromobenzene; 1,2,4,5-tetrachlorobenzene, 1,2,4,5-tetrabromobenzene, 1,2,3 5-tetrachlorobenzene, 1,
Examples thereof include tetrahalobenzenes such as 2,3,5-tetrabromobenzene; alkyl-substituted trihalobenzenes and tetrahalobenzenes; and mixtures thereof. Among these, 1,2,4-trihalobenzene and 1,3,5-trihalobenzene are preferable from the viewpoints of economic efficiency, reactivity, physical properties of the produced PATE, and the like.

Examples of the monohalo aromatic compound include monohalobenzenes such as chlorobenzene and bromobenzene; substituted monohalobenzenes such as 3-chlorotoluene and 1-chlorotoluene; monohalonaphthalenes such as 1-chloronaphthalene and 2-chloronaphthalene. 3-chlorobiphenyl, 1-
Monohalobiphenyl such as chlorobiphenyl; monohalobenzoic acid such as 3-chlorobenzoic acid; monohalobenzophenone such as 3-chlorobenzophenone; monohalodiphenyl sulfone such as 3-chlorodiphenyl sulfone; and the like. Among these, monohalobenzenes are particularly preferable from the viewpoint of economy and reactivity. In addition to the above raw materials, a polymerization aid such as an alkali metal carboxylate may be appropriately used, if desired.

The details of the polymerization method adopted in the present invention are as follows. (1) First-stage polymerization step The first-stage polymerization step includes charging of raw materials, adjustment of the amount of coexisting water, and heating polymerization step. In the polymerization of PATE, the coexisting water content is within the range of 30 to 240 mol (water / alkali metal sulfide molar ratio = 0.3 to 2.4) based on the charged amount of alkali metal sulfide of 100 mol. Adjust so that In order to adjust the coexisting water content of the reaction system,
Before starting the polymerization, for example, an excessive amount of water is distilled out from a mixture containing an organic amide solvent and an alkali metal sulfide, or water is added in some cases.

In the first-stage polymerization step, the amount of coexisting water is 30 to 2 per 100 mol of the alkali metal sulfide charged.
The amount is adjusted to 40 mol, preferably 50 to 210 mol,
More preferably, it is 100 to 200 mol. In the first-stage polymerization step, when the amount of coexisting water is too small, an unfavorable reaction such as a decomposition reaction of the produced polymer easily occurs, and conversely,
If it is excessive, the polymerization reaction may take a long time, and further the decomposition reaction of the produced polymer or solvent may occur. 90 to 120 moles of dihaloaromatic compound per 100 moles of alkali metal sulfide charged (dihaloaromatic compound / alkali metal sulfide mole ratio = 0.90 to 1.20), preferably 95 to 110, particularly It is preferably charged in the range of 98 to 103, and the polyhaloaromatic compound having 3 or more halogen substituents is charged in the range of 0.1 to 5.0 mol, preferably 0.2 to 4.0 mol. .

Polyhaloaromatic compounds having three or more halogen substituents are used to introduce ultra high molecular weight components into the polymer to improve flash properties. However, when a large amount of polyhaloaromatic compound having 3 or more halogen substituents is used, the melt viscosity of the produced polymer is increased, which makes it unsuitable for injection molding. Therefore, it is preferable to partially form a component having a relatively low molecular weight to ensure fluidity suitable for injection molding.

For this purpose, for example, a method of using a dihaloaromatic compound in a stoichiometrically excess or underabundance within an appropriate range with respect to the amount of the alkali metal sulfide charged,
A method of replacing a part of the dihalo aromatic compound with a monohalo aromatic compound, a method of using p-dihalo aromatic compound as a main component and a small amount of o- and / or m-dihalo aromatic compound in combination, As a part, it is effective to use a dihaloaromatic compound having an electron-donating substituent such as a phenoxy group and to shorten the polymerization time in the subsequent polymerization step.

Among the above methods (1) to (5), particularly preferred embodiments are as follows. In the above method, the monohalo aromatic compound is 0 to 20 mol, preferably 0.1 to 10 mol based on 100 mol of the alkali metal sulfide charged.
The method of using in a molar ratio is preferred. In order to generate a low molecular weight component that improves the fluidity of PATE, this ratio is preferably 0.1 mol or more. If this ratio exceeds 20 mol, the mechanical properties of the produced PATE may be unsatisfactory. In addition, the combined use of an appropriate amount of a monohalo aromatic compound is generally advantageous in that the melt stability of the produced PATE is further improved.

In the method (1), p-dihalobenzene and o-dihalobenzene are used as the dihaloaromatic compound in the first-stage polymerization step (1), and the o-dihalobenzene is added in an amount of 100 mol of an alkali metal sulfide. Based on 0.1 to 10 mol, more preferably 0.2
The method of using it at a ratio of 5 mol is preferable. Instead of o-dihalobenzene, or together with o-dihalobenzene, m-dihalobenzene may be used. Further, these p-, o- and m-dihalobenzenes may be substituted dihalobenzenes. If this ratio is less than 0.1 mol, the low molecular weight component that improves the fluidity of PATE may be insufficient, and if it exceeds 10 mol, the product P
The mechanical properties of ATE may be unsatisfactory.

In the method (1), p-dihalobenzene and dihalodiphenyl ether are used as the dihaloaromatic compound in the first-stage polymerization step (1), and the dihalodiphenyl ether is added in an amount of 100 mol of an alkali metal sulfide. The method of using it in a ratio of 0.1 to 10 mol, more preferably 0.2 to 5 mol, is preferred. These dihalobenzenes and dihalodiphenyl ethers may have a substituent. If this ratio is less than 0.1 mol, the low molecular weight component that improves the fluidity of PATE may be insufficient, and if it exceeds 10 mol, the mechanical properties of the resulting PATE may be unsatisfactory. . The organic amide solvent is usually 0.2 to 5 kg (organic amide / mol / mol of alkali metal sulfide).
Alkali metal sulfide = 0.2 to 5 kg / mol) is preferably used.

A mixture having a coexisting water content and a monomer composition ratio within a predetermined range according to the above-mentioned polymerization recipe is subjected to pre-stage polymerization under the following conditions. 150 ~ 270 ℃ the mixture
At a temperature of at least 1 hour, usually 1 to 15 hours to carry out polymerization to form a prepolymer. If the reaction temperature in the first-stage polymerization is too low, the reaction rate is too slow and it takes a long time. On the contrary, if it is too high, the produced PATE and the decomposition of the solvent are likely to occur.

(2) Second-stage polymerization step After the completion of the first-stage polymerization, the coexisting water content of the reaction system is adjusted to a ratio of 245 to 800 mol based on 100 mol of the charged amount of alkali metal sulfide in the first-stage polymerization. Adjust to.
The adjustment of the coexisting water content is usually performed by adding a calculated amount of water to the reaction system. By adjusting the amount of coexisting water within the above range, the liquid-liquid phase separation state of the reaction system is formed or the stable formation of the phase separation state is promoted. That is, when an appropriate amount of water coexists in a high temperature reaction system, a liquid phase mainly containing a PATE prepolymer (polymer rich phase) and another liquid phase (polymer dilute phase)
Separate into phases. By heating the reaction system while maintaining such a liquid-liquid two-phase separation state, the degree of polymerization of the polymer can be effectively increased. If the amount of coexisting water is too small, the liquid-liquid phase separation will be insufficient, and if it is too large, the polymerization reaction will take a long time.

In the latter-stage polymerization step, the reaction is carried out at a temperature of 230 to 280 ° C. for at least 0.5 hours, usually 0.5 to 15 hours. The reaction temperature is particularly preferably 250 to 270 ° C. The polymerization time is preferably 0.5 to 10 hours,
More preferably, it is about 1 to 5 hours. If the polymerization time is too short, the degree of polymerization of the polymer will be insufficient, and if it is too long, the decomposition reaction of the produced polymer or solvent will easily occur. In addition, when there is a possibility that the produced polymer is agglomerated,
As disclosed in JP-A-63-46228, a method of temporarily lowering the temperature on the way and then raising the temperature again to continue the polymerization is effective.

(3) Recovery Step After completion of the second-stage polymerization, the reaction mixture is cooled under high-speed stirring until the temperature becomes equal to or lower than the glass transition temperature of the produced polymer, and the produced polymer is recovered in a granular form. If the stirring speed is slow, the produced polymer may be agglomerated. Since the melt viscosity of the PATE of the present invention is highly dependent on the shear rate, it is desirable to lower the temperature at a high shear rate such that a high shear stress is applied, in order to prevent agglomeration. The stirring speed for recovering the produced polymer in the form of granules can be appropriately determined according to the size of the reactor, the amount of the reaction mixture, the shape of the stirrer, and the like.

After cooling, the slurry of the reaction mixture containing the granular PATE is used as it is or after being diluted with water or the like, and filtered to separate the granular solid content. Next, the granular solid content is washed with water, an organic solvent, or the like by a conventional method, and dried to recover the granular PATE. The PATE thus obtained has an average particle size of 0.1 to 4.0 m.
It is a granular polymer of m, preferably about 0.2 to 2.0 mm.

The PATE of the present invention has an appropriate melt viscosity, has a high melt flowability and a high shear rate dependence of the melt viscosity, has good burr characteristics, and is excellent in mechanical properties.
It is particularly suitable for injection molding. In addition, the PA of the present invention
Since TE has excellent toning property and melt stability, melt processing other than injection molding is possible, and TE can be used for various purposes. Further, the PATE of the present invention can be used by blending it with various fillers, thermoplastic resins, thermosetting resins, elastomers, etc., if desired.

Resin Composition When the PATE of the present invention is used for injection molding, the PATE
ATE 25-98% by weight and fibrous filler 2-75% by weight
It is preferable to use as a resin composition containing. If desired, an inorganic filler other than the fibrous filler may be added in an amount of 0 to
It may be further contained in the composition at a ratio of 70% by weight. In addition, various additives such as stabilizers, colorants and lubricants can be appropriately added as desired. A molded product obtained by injection molding of such a resin composition has a bending strength of 15 kg / mm ² or more, preferably 18 k
g / mm ² or more, more preferably 20 kg / mm ² or more, Izod impact strength of 5 kg · cm / cm or more, preferably 6 kg · cm / cm or more, more preferably 6.5.
It is desirable to have physical properties of kg · cm / cm or more.

Examples of the fibrous filler include glass fiber, carbon fiber, aramid fiber, potassium titanate fiber, silicon carbide fiber, wollastonite and the like. Examples of the non-fibrous inorganic filler include carbon black, titanium oxide, calcium carbonate, silica, alumina, lithium carbonate, iron oxide (including ferrite), molybdenum disulfide, graphite, glass beads and the like. With these fillers, for example, aminosilane, mercaptosilane,
Various coupling agents such as epoxysilane can be used. The resin composition of the present invention can be applied not only to injection molding but also to extrusion molding and the like.

[0052]

EXAMPLES The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. The methods for measuring the physical properties are as follows.

Method for measuring physical properties (1) Hunter whiteness (%) A polymer sample (neat resin) was melted under pressure at 310 ° C. for 30 seconds using a hot press and then rapidly cooled to a thickness of about 0.3 mm. An amorphous sheet was prepared and Hunter whiteness was measured using a color difference meter [Color Ace manufactured by Tokyo Denshoku Co., Ltd.].

(2) Weight average molecular weight With respect to the polymer sample, the differential molecular weight distribution curve by GPC was measured under the following conditions to calculate the weight average molecular weight. Column: SHODEX AT 80M / S 2 in series Solvent: 1-Chloronaphthalene Flow rate: 0.7 ml / min Column temperature: 220 ° C Sample concentration: 0.05 wt% Injection amount: 200 μl Detector: Hydrogen flame ionization detector (FID) Molecular weight calibration sample: standard polystyrene and

[0055]

[Chemical 3] Data processing: Chromatopack C-RAX (Shimadzu)

(3) Melt viscosity (η ^* ) The melt viscosity (η ^* ₁₀₀₀ ) of the polymer is 0.50 mm inside diameter.
It is the melt viscosity measured at 316 ° C. and a shear rate of 1000 (1 / sec) using a capillograph equipped with a φ, 5.00 mm long nozzle. The melt viscosity (η ^* ₁₀₀ ) was measured at 316 ° C using the same capillograph, and the shear rate was 100.
It is the melt viscosity measured at (1 / sec). (4) Dependence of melt viscosity on shear rate (η ^* ₁₀₀ / η ^* ₁₀₀₀ ) From the measurement value of (2) above, the ratio of melt viscosity (η ^* ₁₀₀ ) and melt viscosity (η ^* ₁₀₀₀ ) was calculated.

(5) Average particle size Measured according to JIS K-0069-31. (6) Bending strength The bending strength was measured according to ASTM D-790. (7) Izod impact strength It was measured according to ASTM D-256 (notched). (8) Burr length (μm) An injection molding machine (IS-25EP manufactured by Toshiba Machine Co., Ltd.) was equipped with a mold having a cavity shown in FIG. 1, and the length was set at a cylinder setting temperature of 300 ° C. and a mold temperature of 140 ° C. Fill the resin up to the 6 mm ear. It was injected at the minimum injection pressure and held for 5 seconds, and the burr length generated in the slit portion having a thickness of 30 μm was measured for the obtained molded product.

[Example 1] An autoclave having a capacity of 10 liters, equipped with a stirrer equipped with a baffle and two sets of four blades (upper downflow, lower upflow), and lined with titanium material, 1.53 kg of sodium sulfide pentahydrate as an alkali metal sulfide and N as a solvent
-Methyl-2-pyrrolidone (NMP) 3kg was charged,
Heat to 200 ° C. and add a mixture of water and NMP to about 1.
45 kg was distilled. Then, a certain amount of NMP, water,
1,2,4-trichlorobenzene (TCB), and p-
Dichlorobenzene (p-DCB) was added and the inside of the autoclave was replaced with nitrogen gas, and then the first-stage polymerization was started.
In the first stage polymerization, after heating at 220 ℃ for 4 hours, 250 ℃
Heated at 1.5 hours. Table 1 shows the ratio of each component and the pre-stage polymerization conditions.

After the completion of the first-stage polymerization, a predetermined amount of water was added and then heated at 255 ° C. for 2 hours to carry out liquid-liquid phase separation polymerization. The polymerization conditions are shown in Table 1. After the completion of the polymerization, the reaction system was cooled to around room temperature while the stirring rate was increased to 400 rpm and the reaction mixture was taken out. After leaving the reaction mixture taken out, the particulate matter was separated by decantation,
The washing with acetone and the washing with water were repeated twice. The washed granules are dried under reduced pressure at 80 ° C for 15 hours to obtain granular PATE.
Was recovered.

Example 2 The raw material formulation and polymerization conditions are shown in Table 1.
Polymerization was performed in the same manner as in Example 1 except that the change was made as shown in FIG. In this Example 2, 1,2,4-TCB and 1,3,5-TC were used as trichlorobenzene.
B was used together.

[Examples 3 to 5] Polymerization was carried out in the same manner as in Example 1 except that the raw material formulation and the polymerization conditions were changed as shown in Table 1. In these examples, monochlorobenzene (MCB) was added.

[Comparative Examples 1 and 2] Polymerization was carried out in the same manner as in Example 1 except that the raw material formulation and the polymerization conditions were changed as shown in Table 1. In these comparative examples, it is considered that the amount of coexisting water in the latter-stage polymerization step is small and liquid-liquid phase separation polymerization does not occur. The raw material formulations and polymerization conditions of Examples 1 to 5 and Comparative Examples 1 and 2 are collectively shown in Table 1. The measurement results of various physical properties are shown in Tables 2 and 3 below.

[0063]

[Table 1]

(* 1) DCB: p-dichlorobenzene (* 2) TCB: trichlorobenzene (numerals indicate substitution positions of chlorine atoms) (* 3) MCB: monochlorobenzene (* 4) DCDPE: 4, 4'-dichlorodiphenyl ether

[Comparative Example 3] 1.37 kg of sodium sulfide pentahydrate and NMP were placed in a 10-liter autoclave.
After adding 4.15 liters and 345 g of lithium chloride, the temperature was raised to 200 ° C. in a nitrogen atmosphere to distill 1.83 liters of a mixture of water and NMP. Then 10
P cooled to 0 ° C and dissolved in 1.5 liters of NMP
-DCB and 1,2,4-TCB are respectively p-DC
B / Na ₂ S = 1.05 (molar ratio) and TCB / p-D
It was added so that CB = 0.008 (molar ratio). Then, it was made to react at 260 degreeC for 3 hours. After the completion of the polymerization, after cooling to room temperature, the solid matter was separated, washed successively with 4.5 liters of pure water and acetone, and dried in vacuum at 100 ° C.
A polymer was obtained.

[Comparative Example 4] p-DCB and 1,2,4-
P-DCB / Na ₂ S = 1.10 for each TCB.
A polymer was obtained in the same manner as in Comparative Example 3 except that addition was made so that (molar ratio) and TCB / Na ₂ S = 0.015 (molar ratio).

[Comparative Example 5] 7.756 mol of sodium sulfide pentahydrate and NM were placed in a 10-liter autoclave.
After adding P31.05 mol and replacing with nitrogen, 204-2
Upon heating to 15 ° C., all water was removed from the mixture by atmospheric distillation except 1 mole of water of hydration per mole of sodium sulfide. In the remaining mixture, 1.00 mol of p-DCB, 1,2,4-TCB0.0 per mol of Na ₂ S used.
08 mol, 0.50 mol of water, and 5.18 mol of NMP were added. Then, it heated at 204-205 degreeC for 2 hours, and also at 265-166 degreeC for 3 hours. The reaction product was cooled, washed with hot water, and dried to obtain a polymer.

<Physical Properties of Polymer> Various physical properties of each PATE sample obtained in Examples 1 to 5 and Comparative Examples 1 to 5 were measured. The results are shown in Table 2. Physical properties of a commercially available cure type PPS (PATE) were measured in the same manner and shown as Comparative Example 6.

[0069]

[Table 2]

[Examples 6 to 10 and Comparative Examples 7 to 12] Compositions containing 60% by weight of PATE and 40% by weight of glass short fibers using the polymer samples of Examples 1 to 5 and Comparative Examples 1 to 6. It was created. As the glass short fibers, a registered trade name “Asahi Fiber Glass GL-HF” (diameter 10 μm, length 3 mm) manufactured by Asahi Fiber Glass Co., Ltd. was used.
Further, 0.2 phr of neopentyl polyol ester was added as a lubricant. A mixture containing PATE, glass fiber, and a lubricant was extruded in a strand shape at a resin temperature of 320 ° C. using a co-directional twin-screw kneading extruder (cylinder diameter: 30 mmφ, manufactured by Plastic Engineering Laboratory Co., Ltd.) and rapidly cooled and cut. , Pellets were prepared.

From each pellet, a cylinder set temperature of 30 was obtained by using an injection molding machine (IS-25EP manufactured by Toshiba Machine Co., Ltd.).
Bending test pieces were prepared at 0 ° C. and a mold temperature of 140 ° C. A part of these test pieces was formed into a test piece for Izod impact test by notching by cutting. Bending properties were measured at 23 ° C. using an autograph (10 tons). The Izod impact test was also measured at 23 ° C. In addition, burr characteristics were evaluated using this pellet. The results of physical property evaluation of the composition are shown in Table 3.

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[Table 3]

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EFFECTS OF THE INVENTION According to the present invention, it has high fluidity and high shear rate dependency, and is excellent in burr characteristics, melt stability, and color matching.
Moreover, branched / uncured PA with improved mechanical properties
A TE and a manufacturing method thereof can be provided. Also,
According to the present invention, a resin composition having excellent physical properties is provided by using this PATE.

[Brief description of drawings]

FIG. 1 is a front view showing the shape of a mold cavity for evaluating burr characteristics.

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[Procedure amendment]

[Submission date] June 1, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0069

[Correction method] Change

[Correction content]

[0069]

[Table 2]

Claims (11)

[Claims] 1. The following repeating unit: (A) Hunter whiteness of 20% or more, (b) weight average molecular weight of more than 200,000 and less than 1 million, and (c) melt viscosity η.
A polyarylene thioether characterized in that ^* ₁₀₀₀ is 20 to 500 Pa · s, and (d) shear rate dependence of melt viscosity η ^* ₁₀₀ / η ^* ₁₀₀₀ is 1.8 to 4.0. [However, the melt viscosity η ^* ₁₀₀₀ is a melt viscosity measured at a shear rate of 1000 (1 / sec) at 316 ° C. using a capillograph equipped with a nozzle having an inner diameter of 0.50 mmφ and a length of 5.00 mm. Shear rate dependence of melt viscosity η ^* ₁₀₀ /
η ^* ₁₀₀₀ is 316 ° C using the above capillograph,
At shear rates of 100 (1 / sec) and 1000 (1 / sec),
It is the ratio of the measured melt viscosities η ^* ₁₀₀ and η ^* ₁₀₀₀ , respectively. ] 2. The polyarylene thioether according to claim 1, which is a polymer having a branched structure derived from a polyhaloaromatic compound having three or more halogen substituents and which is not cured. 3. The polyarylene thioether according to claim 1, which is a granular polymer having an average particle size of 0.1 to 4.0 mm. 4. A polyarylene thioether having a bending strength of 15 kg / mm ² or more when injection-molded into a resin composition obtained by kneading the polymer with glass short fibers having an average diameter of 10 μm at a ratio of 40% by weight, and Izod Impact strength is 5
The polyarylene thioether according to any one of claims 1 to 3, which is capable of giving an injection-molded product having physical properties of kg · cm / cm or more. 5. The polyarylene thioether according to claim 1 in an amount of 25 to 98% by weight and the fibrous filler in an amount of 2 to 75% by weight.
A resin composition comprising: 6. A polyarylene having a branched structure by reacting an alkali metal sulfide with a dihaloaromatic compound in a water-containing organic amide solvent in the presence of a polyhaloaromatic compound having three or more halogen substituents. In the method for producing a thioether, the following steps (1) to (3) are sequentially performed.
A method for producing a polyarylene thioether, characterized by comprising: (1) First-stage polymerization step Based on the charged amount of alkali metal sulfide of 100 mol, 90 to 120 mol of dihalo aromatic compound, 0 to 20 mol of monohalo aromatic compound, and 3 or more halogen substituents. 0.1 to 5.0 polyhalo aromatic compounds
It is charged at each molar ratio and the coexisting water content is 30 to 24.
Keep at 0 mole ratio and at least 1 at 150-270 ° C
Heat for hours to form a prepolymer. (2) Second-stage polymerization step By adjusting the amount of coexisting water in the reaction system containing the produced prepolymer so as to be a ratio of 245 to 800 mol based on 100 mol of the charged amount of alkali metal sulfide, Maintaining a liquid-liquid phase separation state mainly composed of a polymer-containing phase and another phase,
Polymerization is continued by heating at 0 ° C. for at least 0.5 hours. (3) Recovery step After completion of the polymerization, the reaction mixture is cooled under high speed stirring to a temperature not higher than the glass transition temperature of the produced polymer, and the produced polymer is recovered in the form of granules having an average particle diameter of 0.1 to 4.0 mm. To do. 7. The production method according to claim 6, wherein in the first-stage polymerization step (1), the monohalo aromatic compound is charged in a proportion of 0.1 to 10 mol based on 100 mol of the alkali metal sulfide charged. 8. The production method according to claim 6, wherein the dihaloaromatic compound in the first-stage polymerization step (1) is p-dihalobenzene. 9. In the first-stage polymerization step (1), the dihaloaromatic compound comprises a mixture of p-dihalobenzene and o-dihalobenzene, and the o-dihalobenzene is added in an amount of 100 mol of an alkali metal sulfide. The production method according to claim 6 or 7, wherein the amount is 0.1 to 10 mol based on the standard. 10. In the first-stage polymerization step (1), the dihaloaromatic compound comprises a mixture of p-dihalobenzene and dihalodiphenyl ether, and the dihalodiphenyl ether is charged with an alkali metal sulfide in an amount of 100.
The production method according to claim 6 or 7, wherein the amount is 0.1 to 10 mol based on mol. 11. A polyhaloaromatic compound having three or more halogen substituents in the first-stage polymerization step (1),
The production method according to any one of claims 6 to 10, which is 1,2,4-trihalobenzene, 1,3,5-trihalobenzene, or a mixture thereof.